EP1154011A1 - Composition d'huile lubrifiante haute temperature - Google Patents

Composition d'huile lubrifiante haute temperature Download PDF

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Publication number
EP1154011A1
EP1154011A1 EP99961304A EP99961304A EP1154011A1 EP 1154011 A1 EP1154011 A1 EP 1154011A1 EP 99961304 A EP99961304 A EP 99961304A EP 99961304 A EP99961304 A EP 99961304A EP 1154011 A1 EP1154011 A1 EP 1154011A1
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EP
European Patent Office
Prior art keywords
high temperature
lubricant composition
weight
base oil
antioxidant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP99961304A
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German (de)
English (en)
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EP1154011B1 (fr
EP1154011A9 (fr
Inventor
Hideto Kamimura
Hiroshi Nagakawa
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
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    • C10M2205/022—Ethene
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    • C10N2040/38—Conveyors or chain belts

Definitions

  • the present invention relates to a lubricant composition for a high temperature. More specifically, it relates to a lubricant composition for a high temperature which is used in a chain, a roller chain, a chain conveyor, a bearing and the like.
  • a lubricant which is used in a chain, a roller chain, a chain conveyor, a bearing and the like is exposed to a high temperature, an amount of a lubricant evaporated greatly influences a life of an apparatus.
  • a lubricant loses an ordinary viscosity under a condition of a high temperature and becomes a thin film, so that an amount of a lubricant evaporated has to be controlled under severer conditions.
  • high-molecular oil with a high viscosity has been used to control an amount evaporated. Although an amount of such oil evaporated is small, a power loss is great, and it is undesirable in view of a total performance of a lubricant.
  • a lubricant for a high temperature of which the amount evaporated in a thin film at a high temperature is controlled and of which the fluidity is maintained for a long period of time has been in demand.
  • the present invention aims to provide a lubricant composition for a high temperature of which the amount evaporated in a thin film at a high temperature is controlled and of which the fluidity is maintained for a long period of time.
  • the present inventors have assiduously conducted investigations, and have consequently found that the aim of the present invention can be achieved by using a specific aromatic ester compound as base oil. This finding has led to the completion of the present invention.
  • the gist of the present invention is as follows.
  • the base oil composition constituting the lubricant composition for the high temperature in the present invention comprises (a) 20 to 100% by weight of the aromatic ester compound represented by the above general formula (I) and (b) 0 to 80% by weight of another base oil.
  • the number of carboxylic acids bound to benzene is preferably 3 or 4.
  • trimellitic acid and pyromellitic acid are preferable.
  • an aliphatic alcohol used in the aromatic carboxylic acid ester a linear or branched alcohol having 6 to 16 carbon atoms is preferable.
  • aromatic carboxylic acid esters may be used either singly or in admixture of two or more types, and a partial ester may be contained in a full ester.
  • any mineral oil type or synthetic oil type that is used as base oil of ordinary equipment oil can be used.
  • the mineral oil-type base oil for example, refined oil which is formed by refining a lubricant fraction resulting from atmospheric distillation or vacuum distillation of paraffin base crude oil, intermediate base crude oil or naphthene base crude oil by an ordinary method such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation refining, sulfuric acid treatment, clay treatment or the like.
  • the synthetic oil-type base oil various substances such as an ⁇ -olefin oligomer, an ethylene- ⁇ -oligomer, a polybutene, a dibasic acid ester, a polyalkylene glycol, a hindered ester, an alkylbenzene, an alkylnaphthalene, a polyether and the like can be used.
  • an ⁇ -olefin oligomer, an ethylene- ⁇ -oligomer, a polybutene or hydrogenated substances thereof are preferable because the fluidity can be maintained for a long period of time.
  • component (b) one type or a mixture of two or more types may be used, and a mixture of mineral oil and synthetic oil may be used.
  • the proportions of the aromatic carboxylic acid ester (a) and another base oil (b) are that component (a) is 20 to 100% by weight and component (b) is 0 to 80% by weight, and preferably component (a) is 30 to 80% by weight and component (b) is 20 to 70% by weight. When component (a) is less than 20% by weight, the effect of the invention is not provided.
  • an amine-type antioxidant and a phenolic antioxidant can be used.
  • an antioxidant containing sulfur and/or phosphorus in a molecule is preferable.
  • amine-type antioxidant examples include monoalkyldiphenylamines such as monooctyldiphenylamine, monononyldiphenylamine and the like; dialkyldiphenylamines such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine and the like; polyalkyldiphenylamines such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine and the like; and naphthylamines such as ⁇ -naphthylamine, phenyl- ⁇ -nap
  • phenolic antioxidant can include monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol and the like; and diphenols such as 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) and the like.
  • antioxidant containing sulfur and/or phosphorus in the molecule can be an additive containing sulfur and/or phosphorus in a molecule and having an antioxidant ability, and it may be added for the other purpose.
  • the antioxidant containing sulfur in the molecule is described.
  • sulfurized oil sulfurized mineral oil, a sulfurized fatty acid, a sulfurized ester, a sulfurized olefin, dihydrocarbyl polysulfide, a thiadiazole compound, an alkylthiocarbamoyl compound, a triazine compound, a thioterpene compound, a dialkylthiodipropionate compound and the like can be mentioned.
  • sulfurized oil is oil obtained by reacting sulfur or a sulfur-containing compound with oil (lard, whale oil, vegetable oil, fish oil or the like), and the sulfur content is not particularly limited. Generally, it is preferably between 5 and 30% by weight. Specific examples thereof include sulfurized lard, sulfurized rapeseed oil, sulfurized castor oil, sulfurized soybean oil, sulfurized rice bran oil and the like.
  • sulfurized fatty acid include sulfurized oleic acid and the like.
  • sulfurized ester include sulfurized oleic acid methyl ester, sulfurized rice bran fatty acid octyl ester and the like.
  • the sulfurized olefin for example, a compound represented by the following general formula (II) R 2 - S a - R 3 (wherein R 2 represents an alkenyl group having 2 to 15 carbon atoms, R 3 represents an alkyl group or an alkenyl group having 2 to 15 carbon atoms, and a represents an integer of 1 to 8).
  • This compound is obtained by reacting an olefin having 2 to 15 carbon atoms or its dimer to tetramer with a sulfurizing agent such as sulfur, sulfur chloride or the like.
  • a sulfurizing agent such as sulfur, sulfur chloride or the like.
  • the olefin propylene, isobutene, diisobutene or the like is preferable.
  • the dihydrocarbyl polysulfide is a compound represented by the following general formula (III) R 4 - S b - R 5 ⁇ (wherein R 4 and R 5 each represent an alkyl group or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and these may be the same or different, and b represents an integer of 2 to 8).
  • R 4 and R 5 therein are alkyl groups, it is called an alkyl sulfide.
  • R 4 and R 5 in the above general formula (III) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various dodecyl groups, a cyclohexyl group, a cyclooctyl group, a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a benzyl group, a phenetyl group and the like.
  • dihydrocarbyl polysulfide examples include dibenzyl polysulfide, various dinonyl polysulfides, various didodecyl polysulfides, various dibutyl polysulfides, various dioctyl polysulfides, diphenyl polysulfide, dicyclohexyl polysulfide and the like.
  • thiadiazole compound for example, 1,3,4-thiadiazole and 1,2,4-thiadiazole compounds represented by the following general formulas (IV) (wherein R 6 and R 7 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and c and d each represent an integer of 0 to 8) are preferably used.
  • thiadiazole compounds can include 2,5-bis(n-hexyldithio)-1,3,4 -thiadiazole, 2,5-bis(n-octyldithio)-1,3,4-thiadiazole, 2,5-bis(n-nonyldithio)-1,3,4-thiadiazole, 2,5-bis(1,1,3,3-tetramethylbutyldithio)-1,3,4-thiadiazole, 3,5-bis(n-hexyldithio)-1,2,4-thiadiazole, 3,5-bis(n-octyldithio)-1,2,4-thiadiazole, 3,5-bis(n-nonyldithio)-1,2,4-thiadiazole, 3,5-bis(1,1,3,3-tetramethylbutyldithio)-1,2,4-thiadiazole and the like.
  • alkylthiocarbamoyl compound for example, a compound represented by the following general formula (V) (wherein R 8 to R 11 each represent an alkyl group having 1 to 20 carbon atoms, and e represents an integer of 1 to 8) can preferably be used.
  • alkylthiocarbamoyl compound examples include bis(dimethylthiocarbamoyl) monosulfide, bis(dibutylthiocarbamoyl) monosulfide, bis(dimethylthiocarbamoyl) disulfide, bis (dibutylthiocarbamoyl) disulfide, bis(diamylthiocarbamoyl) disulfide, bis(dioctylthiocarbamoyl) disulfide and the like.
  • triazine compound examples include 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol and the like.
  • examples of the thioterpene compound include a reaction product of phosphorus pentasulfide and pinene.
  • examples of the dialkylthiodipropionate compound include dilaurylthiodipropionate, distearylthiodipropionate and the like.
  • a zinc dialkyldithiocarbamate Zn-DTC
  • Mo-DTC molybdenum dialkyldithiocarbamate
  • a lead dialkyldithiocarbamate a tin dialkyldithiocarbamate, sodium sulfonate, calcium sulfonate and the like
  • Zn-DTC zinc dialkyldithiocarbamate
  • Mo-DTC molybdenum dialkyldithiocarbamate
  • a lead dialkyldithiocarbamate a tin dialkyldithiocarbamate
  • sodium sulfonate calcium sulfonate and the like
  • Typical examples include phosphoric acid esters and amine salts thereof.
  • the phosphoric acid esters include a phosphoric acid ester, an acid phosphoric acid ester, a phosphorous acid ester and an acid phosphorous acid ester represented by the following general formulas (VI) to (X).
  • R 12 to R 14 each represent an alkyl group, an alkenyl group, an alkylaryl group and an arylalkyl group having 4 to 30 carbon atoms, and R 12 to R 14 may be the same or different.
  • the phosphoric acid ester includes a triaryl phosphate, a trialkyl phosphate, a trialkylaryl phosphate, a triarylalkyl phosphate, a trialkenyl phosphate and the like. Specific examples thereof include triphenyl phosphate, tricresyl phosphate, benzyldiphenyl phosphate, ethyldiphenyl phosphate, tributyl phosphate, ethyldibutyl phosphate, cresyldiphenyl phosphate, dicresylphenyl phosphate, ethylphenyldiphenyl phosphate, diethylphenylphenyl phosphate, propylphenyldiphenyl phosphate, dipropylphenylphenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyldiphenyl phosphate, dibuty
  • the acid phosphoric acid ester examples include 2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate and the like.
  • the phosphorous acid ester examples include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri(nonylphenyl) phosphite, tri(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, trioleyl phosphite and the like.
  • acid phosphorous acid ester examples include dibutylhydrogen phosphite, dilaurylhydrogen phosphite, dioleylhydrogen phosphite, distearylhydrogen phosphite, diphenylhydrogen phosphite and the like.
  • the amines forming amine salts with these include a mono-substituted amine, a di-substituted amine and a tri-substituted amine represented by the general formula (XI) R 15 m NH 3-m (wherein R 15 represents an alkyl group or an alkenyl group having 3 to 30 carbon atoms, an aryl group or an arylalkyl group having 6 to 30 carbon atoms or a hydroxyalkyl group having 2 to 30 carbon atoms, m represents 1, 2 or 3, and when R 15 is plural groups, plural R 15 's may be the same or different).
  • an alkyl group or an alkenyl group having 3 to 30 carbon atoms may be linear, branched or cyclic.
  • examples of the mono-substituted amine can include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, benzylamine and the like.
  • di-substituted amine examples include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl-monoethanolamine, decyl-monoethanol amine, hexyl-monopropanolamine, benzyl ⁇ monoethanolamine, phenyl ⁇ monoethanolamine, tolyl ⁇ monopropanol amine and the like.
  • tri-substituted amine examples include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl-monoethanolamine, dilauryl ⁇ monopropanolamine, dioctyl ⁇ monoethanolamine, dihexyl ⁇ monopropanolamine, dibutyl ⁇ monopropanolamine, oleyl ⁇ diethanolamine, stearyl ⁇ dipropanolamine, lauryl-diethanolamine, octyl ⁇ dipropanolamine, butyl ⁇ diethanolamine, benzyl-diethanolamine, phenyl-diethanolamine, tolyl ⁇ dipropanolamine, xylyl-diethanolamine, triethanolamine, tripropanolamine and the like.
  • antioxidant containing phosphorus and a halogen atom can include a chlorinated phosphoric acid ester.
  • antioxidant containing sulfur and phosphorus in the molecule can include phosphorus sulfide oil, a phosphorus sulfide olefin, a thiophosphoric acid ester (thiophosphite and thiophosphate) and the like.
  • a thiophosphite (alkylaryl type) and a thiophosphate (alkylaryl type) are preferable.
  • antioxidant containing sulfur, phosphorus and a metal can include dithiophosphoric acid salts such as zinc dithiophosphate (Zn-DTP), molybdenum dithiophosphate (Mo-DTP), lead dithiophosphate, tin dithiophosphate and the like.
  • dithiophosphoric acid salts such as zinc dithiophosphate (Zn-DTP), molybdenum dithiophosphate (Mo-DTP), lead dithiophosphate, tin dithiophosphate and the like.
  • antioxidants 2,6-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, Zn-DTP(alkylaryl type), a thiophosphite (alkyl type) and a thiophosphate (alkylaryl type) are preferable.
  • antioxidants can be used either singly or in combination.
  • the preferable mixing amount of the above antioxidant is in the range of 0.1 to 10% by weight based on the total amount of the composition.
  • the mixing amount is less than 0.1% by weight, the aim of the present invention is not fully exhibited.
  • it exceeds 10% by weight the improvement in the effect is sometimes not observed even with this amount, and the solubility in base oil is sometimes decreased.
  • the more preferable mixing amount is in the range of 1 to 7% by weight.
  • the lubricant composition for the high temperature in the present invention can contain various known additives such as a rust-proofing agent, a detergent-dispersant, a metal inactivator, a defoamer and the like as required unless the aim of the present invention is impaired.
  • Examples of the rust-proofing agent can include a metal sulfonate, a succinic acid ester and the like.
  • detergent-dispersant can include a metal sulfonate, a metal salicylate, a metal finate, a succinic acid. imide and the like.
  • metal inactivator examples include benzotriazole, thiadiazole and the like.
  • defoamer examples include methyl silicone oil, fluorosilicone oil, a polyacrylate and the like.
  • the kinematic viscosity at 40°C of the lubricant composition for the high temperature in the present invention is adjusted to 10 to 50 mm 2 /s in order to achieve the aim. It is more preferably in the range of 50 to 320 mm 2 /s.
  • the lubricant composition for the high temperature in the present invention is preferably used when the temperature exceeds 150°C in a time of more than 50% of the use period.
  • base oil was mixed with an antioxidant to prepare a lubricant composition.
  • the mixing was conducted by adjusting a viscosity of an ⁇ -olefin oligomer, whereby the kinematic viscosity at 40°C was all adjusted to 220 mm 2 /s.
  • a thin film residue test was conducted in the following manner. Further, a container was inclined, and the fluidity at that time was visually evaluated. The results are shown in Table 1.
  • the amount of the residue was measured at 200°C for 24 hours using a container and a constant-temperature air bath indicated in a lubricant heat stability test of JIS K 2540. This was expressed in terms of percentage, and defined as a residue ratio. By the way, 10 liters/hr of air was always caused to flow in during the measurement.
  • a lubricant composition for a high temperature of which the amount evaporated in a thin film at a high temperature is controlled and of which the fluidity is maintained for a long period of time can be provided.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
EP99961304A 1998-12-25 1999-12-22 Composition d'huile lubrifiante haute temperature Expired - Lifetime EP1154011B1 (fr)

Applications Claiming Priority (3)

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JP37048198A JP4049916B2 (ja) 1998-12-25 1998-12-25 高温用潤滑油組成物
JP37048198 1998-12-25
PCT/JP1999/007202 WO2000039256A1 (fr) 1998-12-25 1999-12-22 Composition d'huile lubrifiante haute temperature

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WO2002064712A1 (fr) * 2001-02-15 2002-08-22 Imperial Chemical Industries Plc Composition lubrifiante pour le travail des metaux
WO2006014950A2 (fr) * 2004-07-27 2006-02-09 The Lubrizol Corporation Compositions lubrifiantes contenant un ester d'un agent d'acylation polycarboxylique
US8530396B2 (en) 2005-11-22 2013-09-10 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joint and constant velocity joint
AU2012261221B2 (en) * 2011-05-26 2016-05-12 KLUBER LUBRICATION MUNCHEN SE & Co. KG High temperature oil
WO2016096074A3 (fr) * 2014-12-17 2016-09-01 Klüber Lubrication München Se & Co. Kg Lubrifiants haute température
WO2016096075A3 (fr) * 2014-12-17 2016-09-01 Klüber Lubrication München Se & Co. Kg Lubrifiant haute température pour les industries alimentaires
EP2975103A4 (fr) * 2013-03-14 2016-11-16 Idemitsu Kosan Co Composition lubrifiante hautes températures

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WO2006014950A2 (fr) * 2004-07-27 2006-02-09 The Lubrizol Corporation Compositions lubrifiantes contenant un ester d'un agent d'acylation polycarboxylique
WO2006014950A3 (fr) * 2004-07-27 2006-03-09 Lubrizol Corp Compositions lubrifiantes contenant un ester d'un agent d'acylation polycarboxylique
US8530396B2 (en) 2005-11-22 2013-09-10 Kyodo Yushi Co., Ltd. Grease composition for constant velocity joint and constant velocity joint
AU2012261221B2 (en) * 2011-05-26 2016-05-12 KLUBER LUBRICATION MUNCHEN SE & Co. KG High temperature oil
EP2975103A4 (fr) * 2013-03-14 2016-11-16 Idemitsu Kosan Co Composition lubrifiante hautes températures
WO2016096074A3 (fr) * 2014-12-17 2016-09-01 Klüber Lubrication München Se & Co. Kg Lubrifiants haute température
WO2016096075A3 (fr) * 2014-12-17 2016-09-01 Klüber Lubrication München Se & Co. Kg Lubrifiant haute température pour les industries alimentaires
EP3372659A1 (fr) * 2014-12-17 2018-09-12 Klüber Lubrication München SE & Co. KG Lubrifiants haute température
EP3372660A1 (fr) * 2014-12-17 2018-09-12 Klüber Lubrication München SE & Co. KG Lubrifiants haute température
EP3375850A1 (fr) * 2014-12-17 2018-09-19 Klüber Lubrication München SE & Co. KG Lubrifiant haute température pour l'industrie alimentaire
EP3375851A1 (fr) * 2014-12-17 2018-09-19 Klüber Lubrication München SE & Co. KG Lubrifiant haute température pour l'industrie alimentaire

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EP1154011B1 (fr) 2005-09-14
EP1154011A9 (fr) 2002-05-15
JP2000192071A (ja) 2000-07-11
JP4049916B2 (ja) 2008-02-20
KR20010110411A (ko) 2001-12-13
CN1179024C (zh) 2004-12-08
WO2000039256A1 (fr) 2000-07-06
CN1332784A (zh) 2002-01-23
USRE39382E1 (en) 2006-11-07
TW531559B (en) 2003-05-11
KR100637961B1 (ko) 2006-10-23
DE69927293D1 (de) 2005-10-20
US6465400B1 (en) 2002-10-15
DE69927293T2 (de) 2006-01-19

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